7-triazinylamino-3-phenyl coumarins



v ma e-,-

--Heim'ich Hiiusennann, Basel, Switzerland, assignor to J. R Geigy A .-G., Basel, Switzerland "The invention concerns new '7-triazinylamino-Bphenyl cqurnarins, processes forthe production thereof and their use for improving the appearance of more oiFlessWyhite carriers in daylight by optically compensating jh e yellowing by blue'fluorescent light. l 'It has been found that valuable *7-triazinylamino-3- phenyl coumarinsare obtained if, in a" 2-.4.=6-t1jihalogen- "1 L3 .5-t riazine,,ahalogen-atom is reactediyith a l-amino- 3-phenyl coumarin wherein the phenyl fradical can be-fur- *ther I substitutednon ionogenically anda Qfu-rther halogen atom -is reacted with 1 an -';'inorganic l or orgam'c: nitrogen base containing-hydrogen whieh can bereplaced atabasic i-initrogenatompthe reactions being performed inaany order -:clesired advantageously in inert organic -orin --inert orsganic/aqueous. solution or suspension-or in the melt and sin: the presence .of .acidabinding agents, (and, intsthe con- --;densation .iproductobtained ,possibly replacing the fhalogenatomof thecyanuric radicaltalsotby ,thehydroxyl group. by means on. alkali, ortby. etherggroups' ,byimeans' of alkali alkoxide, phenoxide or phenyl mercaptide oribyran zam ne radical bywmeans of an. inorganicor organic-fnitrogen base having a hydrogen .atomnwhiclrcan-ebe replaced at a basic nitrogen atom. ,The components should be so chosen that the aromatic nuclei cgntain neither ionogenic substituents such as acid groups, e.g sulphonic acid or earboxylgro ps, nor auxochrogies, for example amino and hydroxyl groups, nor chrompphores.

The end products according to the present invention correspond to thegeneral Eormulal:

wherein R1 andiR each, rfeprese ro t rou c sistin by iphafie y a p a ia 229 1921 y l dicahmdrartoha 9y X r p s ts,a.-m mb r..sel ct in o h l e hydr yl, a 92 i, mononuclearar lme capt hdfit er in which radical R and-R have the same meaning as R; and R above, and

A represents an .isocyelic-aromatic mongnuclear aryl radical, the aromatic nuclei being free-from chromo- States ateut lTheiphenyl radical of the 7-.amino coumarin compounds used according :to the present invention can contain as noh-ionogenic substituents, for example aliphatic groups such as methyl, ethyl, isopropyl, tert. hutyl, isobutyl, 1.2-

tetrameth'ylene groups; .alicyclicsubstituents such {as the cyclohexyl group; raraliphatic suhstituents such as the 'benzyl group; halogens such as fluorine, chlorine or bromine; ctherlgroupstsuch as methoxy, ethoxy, butony, .henzyloxy orphjenorgy groups. ;H wever, the unsubsti- 10 tuted orlth methyl or hlorin substit e PhehYLrhd is preferred. The p du t n of su .:ami 9: :p eh

eoumarins used according to the present -invention is :Q i fly: amo ia' bnti qs ih al h dmzy amine h dra i is us 'a iaprsa ii it n as wh i rea te acc rdi t the Pre en nv n i .Ch fl a inhme r y l al hat e an' rq na s l r y li human and tea ada m n are us a a eni nitroatm usav i -in a h ta ewm w i h. an-li ame ,ata basic nitrogen atom, for example monoand dia ylamines such 'as' inethylarr' ine, ethylamine' butyloct ylamiiie, dodieciylam i'ne', hexadecylamine, Jie'xa- Ytlecenylamine, ioc tadecylamine, dietliylainine, fdib 'l ltyl- 'tylaniiiie,methyldodecylaininmflir vdroxve'thhydroxypropylamiiie, trihydroxy-te tiaryb lfyll mine, his-hydroxyet'hylamine,' cyclohexylamirie, dicycloyl in he', ydroxyyclph ylaminei a alinha ic p'r mars" and seco ry n t b s s su h 'bien yl- .amaa tn-meth xyhen ryla in i h'zv i 19; hvsl'm- .a a't'ed heterobys icafi i l s has d zc lie, J 2 -a noftetrlahydropyrimidine," piperidine, fr'nor'p l iol e;

r j, a iph i eal phifip .al c y q inhat a sew. ar' ami e 'i' as;' b xam e N er" p 's-bi yl-ehai ami 'N nz h. et iae N'Y1 Y1' hiii5l min final as aad qqnder a 'ti am a t a fl 9 t e benzene; series such as a nq n ene; amino'methyl benzenes', -aminochloroben' zenes, aminoalkoiiybenzene, amijn opli'enol polyglycol ethers, Y N-alkylaininobenie'iies, IN- 40 jalkylaniindallgyl'@benienes, N-a'lkylamino niet'hoitybenzenes, hailcgehbehzeiis, B hydroiyethoxy=arniiiobenzenes and amines of the heterocyclic series such as-Q annepyridine,-S-aniino-LZAJIiaiole, 'za'r iiilebenz thia'z le. e rhe replacement of the third halogen atom 53 hydronyl can be leiiected with'alkaliicarbonates arena-al ali hy- -droxides as well as earthalkali'hydroxides'. Ether groups are introduced advantageouslyin' an excess of-the organic hydroxyl or mercapto compound used in the reaction as alkali metal salt. The reaction of the last halogen atom with a primary or secondary organic amine-is performed 5 advantageouslvinjh excess thereof, which amine acts as acid bindingkagent whi st the usual inorganic or organic acid binding agents can be'use'd-for the reaction of the first and second halogen atom, such as -alkali bicarbonates, alkali carbonates or tertiary nitrogen bases such as triethylamine. If in the first and scond'reactions,

[low aliphatic amines are used, then the third" halogen can also be reacted with the-7-amiiio-3-phenyl cournarin .lin the solution or melt athiglier temperatures. 'For the grestjthe conditions usual for such reactions are kept; that is the'first halogen atom is. reacted at a' relatively low temperature, the second atmedium temperatures and the thirdv at higher temperatures. The most favourable .tem m-peraturerrange is dependent on the. reactivity of .the amine s-uisedfor thereaction.

-Lovw lietones such ,as acetone, methylethyl ketone, di-

butylhetone, cyclohexanone, xylenes, chlorobenzene; .ethers such .as glycol ,diethyl ether, dioxan, anisol, PhnQ lQWer at y a id mid s u h as f nnamid Me hy fQlIflfiiflMQ- flififiihy a e amide; al l me hy 7 ,.sulph0nide can be .used as inert,.organic solvents vand "a ntswe witeaQt n -stmn bas ami e als alcohols such as ethanol, isopropanol, butanol, ethylene 1.3 .5-triazinylamino-(6) ]-3-phenyl glycol monomethyl or monoethyl ethers can be used. The 7-triazinylamino-3-phenyl coumarins according to the present invention are colourless to weakly yellow coloured powders having a clear higher melting point. They have a strong green-blue, blue to violet fluorescence in ultraviolet light and in daylight in organic and organic/ aqueous solution and are suitable therefore for use as optical brightening agents.

In UV-containing light, for example in daylight, they improve the appearance of more or less colourless or white carriers by optically compensating the yellowing by the blue fluorescent light. For this purpose, they are incorporated in small amounts, e.g. of 0.001 to 1.0%, into the carrier's. Because of their hydrophilic properties and often because of their slight water solubility, end.

products having primary or low secondary amino groups, in particular having low monohydroxy-alkylamino groups at the triazine ring, can be used in aqueous dispersion.

For example from a neutral solution of fine washing agents such as alkylaryl sulphonates, fatty alcohol sulphonates or acylamino fatty acids containing higher fatty acid radicals, they draw ontosynthetic and natural polypeptide fibres such as synthetic polyarnide and polyurethane fibres, wool, silk, also onto cellulose acetate fibres of the monoto tri-acetate type, onto polyester fibres, some of them also draw well onto cellulose fibres and they very much improve the appearance of the treated material in daylight.v

The end products according to the present invention having tertiary amino groups at the triazine ring, in particular those having medium to higher hydrocarbon radicals as nitrogen substituents, are suitable for the brightening of many synthetic materials on being incorporated in the mass, for

example for the brightening of vinyl polymers such as polyvinyl chloride, polystyrene, polyethylene, polyacryl and polymethacryl acid esters, polyacrylonitrile. They can be incorporaled into these substances either in thermoplastic condition or, possibly, in plasticisers. The optical brightening agents according to the present invention are distinguished in polymeric synthetic 'materials by an extraordinary fastness to light in addition to their good brightening efiect. They can be used for the brightening of synthetic detergents, for improving the appearance of lipsticks or creams, of fats, waxes and paraflines.

The following examples illustrate the invention. Where not otherwise stated, parts are given as parts by weight. The temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is as that of grammes to cubic centimetres.

47.4 parts of 7-amino-3-phenyl coumarin are suspended in 500 parts of 2.4-bis-diethylamino-6-chloro-1.3.5-triazine (Am. Soc. 73 2982 (1951)) and the suspension is heated for 1 hour at l60-170 while stirring. A thickly liquid, pale beige paste is obtained. It is cooled, the product is filtered oif under strong suction and well washed with benzene. After drying, 90-100 parts of a pale yellowish powder containing halogen are obtained. It is the hydrochloride of the 7-[2l4-bis-diethylarninocoumarin formed. The product can be purified by recrystallisation from dimethyl formamide or alcohol. The pure compound melts on decomposition (splitting off of HCl) at 245- 247" and in alcoholic solution it has a strong blue fluorescence. amino-1.3.5-triazinylamino-(6)l-3-pheny1 coumarin, the

hydrochloride is dissolved in hot dimethyl formamide and an excess of aqueous ammonia or sodium acetate solution is added; the product can be isolated by precipitating with water or by evaporating in the vacuum. The free base is a yellowish powder and it crystallises from toluene in pale yellow crystals which melt at 209-210". In organic solution the new compoundfluoresces intensive blue to blue-violet. Both the free base and its hydrochloride are excellentlysuitable for the brightening of various organic substances, in particular synthetic materials of polymeric character.

0.003 partof the compound obtained according to this example are thoroughly mixed with 100 parts of polystyrene powder'and then homogeneously mixed on a set of mixing rollers at 130. The hard plate obtained is broken up and'the product is further worked up by injection moulding or by presses. The synthetic product obtained has a considerably more white appearance in daylight than a comparative product produced under analogous conditions but without the brightening agent. An opaque product is obtained by working up 0.015

.part of brightening agent, 100 parts of polystyrene powder and 2 parts of titanium dioxide (Anatas) in the manner described above. The opaque product also has a considerably more white appearance than the correspond- .ing product without the addition of brightening agent.

100 parts of high pressure polyethylene in the form of granulate are mixed dry at room temperature with 0.05 part of 7-[2.4-bis-diethylamino-1.3.5-triazinylamino-(6)]- 3-phenyl coumarin and the mixture is then worked up in an extruder at 1 20-l30 into a tube. The tube obtained is considerably more white than the product produced To convert into the free 7-[2.4-bis-diethyl- 2S-.i parts" of 7-anrino-3'-(p-methylphenyi) coumarin and 50. parts of' 2.4 -bis-diethylarninoidrchloro 1.3r5 tri 'azi'ne" (Am. Soc. 73 2982 (1951)) are boiled unde'r' re.- fiuxfor 6 hours in 250. parts of dim'e'thyl rermamiae while stin'ing; The clear, brownish reaction solution is diluted with 250 parts Of'l alcohol and on the addition of excessconcentrated hydrpchloric acid, the hydrochloride of 7- E2.4'-bis"-diethy1arnino l'.35-tr'iazinylamino (fi)fl 3 (p'=n'"iethy1'phenyl)-coumarfnf separates in the" of an almost colourless precipitate. 40 4i; parts: of the crude chlorohydrateare obtained. It can be obtained in armlytically pure form by recryst allis ing froiriijiniethyl fbrrnamid'e (M.P. 255-260 while splitting ofiHQl'); In alcoholic solution, this produc't alst'r a -.1 splendid blhe fluorescence. -I-oproduce the free base, the hydrochlo ride is suspended in about times the amount of dimethyl formamide and a concentrated aqueeus solution of sodium acetate (150-200- parts of. crystailisedsodium acetate to 510 parts of hydrochloride) is added atwater bath; temperature. The product" can be isolated either by precipitating with water or by distilling oh. the dimethyl formamide/water mixture; The compound recrystallisedq from toluene or benzene: forms yellowish crystals which melt at 185-186 The new coumarin derivative dissolves in many organic solvents with: a greenish-blue toblue-violet fluorescence. 'I-he compound is also excellently suitable: for the brightening? of organic substances. 7 If in this. example the 25.1 partsof 7-amino-3 -(p-methpIphe'n'yl-.):-coumarin.isrreplacedv by 27.2 parts of. 7.-"amino- 3-(p-chlor'o'phenyl)-coumarin, then 7-[2.4-bis-diethylamino -'1.3..5-- triazinylamino (6) -3-(p-chldrophenyl) c oumar in is obtainedin an analogous manner. M.P. 198 199". fluorescent properties analogous to the p-tolyl derivative and is also suitable fbr the brightening of organic materials. r v

0.004 part of the 7'-E2.4 bisdiethylamine l.3 .5-tri azinylamino-(6) J-3-(p-methylphenyl) -coumarin obtained are dissolved in 100 parts of monomeric methacrylic acid methyl ester, 0.1 part of lauroyl peroxide are added and the whole is poured into the desired form. The mixture is polymerised by heating for 24 hours at 60 and then tempered for 1 hourat 160. Due to its vivid blue fluorescence in daylight, the glass clear resinous body obtained has a more brilliant appearance than a. synthetic resin produced without the addition of the brightening agent.

0.01 part of 7-[2.4-bis-diethylamino-1.3.5-triazinylamino-(6)]-3-(p-chlorophenyl)-coumarin and 0.1 part of benzoyl peroxide are dissolved in 1 00 parts of a monomeric unsaturated ester of the marketed name Palatal 5. The solution is poured between glass plates and polymerised for 1 hour at" 80. A polyester resin which fiuoresces blue-violet in ultra-violet light is obtained. which has a more brilliant aspect in daylight than a resin plate produced without the addition of brightening agent. This unsaturated polyester resin can also be produced by polymerising cold for several hours. In this case too, the brightening agent has a good eifect.

In addition to the two compounds mentioned in this example naturally also the products as described for example in Example 1 can be used for the treatment of these resins.

' 18.45 parts of cyanuric chloride are dissolved in 1000 This product containing chlorine also has parts by volume of acetone and 500 parts of broken up ice'are added whilestir'ring. An acetone solution of 23.7

. 5 parts of 7-amino-3-phenyl courriarih. is. poured withih about 10 minutes to the mixture so obtained while can; ing with ice and stirring and the hydrochloric manua atedis neutrali'sed by the drop'wise'. additionflofv 15% aqueous sodium carbonate sofution. After the addition offth'e amine, the pale yellowish suspension is stirred at 0 5 while the reaction is kept neut-ra'l with sodium carbonate solution until a sample reacted with nitrous acid shows that there'isno more. diazonium compound present. The reaction is completed ai ter 2-3 hours. In this way 7 [2141- dichloro R35 triazinylamino-(6)l-3-phenyl coumarin is obtained as a yellowish suspension. The dichloro-derivative is then reacted with diethylamine without being isolated as follows:

An about 5.0% aqueousvsolution of. 115.5 parts of diethylamine is added at (I-lO" while. stirring. within 30 minutes andl'th'e mixture obtainedis thenv stirred overnight. at room temperature. 0a completion. of the reaction. the reaction mixture is heated for 1. hour at 50-60", then cooled to. (5-10? and. the yellowish precipitate is filtered off. After washing: with. water and drying in the vacuum at 70-80, 35-40 parts. of a. yellowish, halogen-containing. powder are. obtained. On recrystalli'sing from toluene, the 7-[2-diethylamin0-4 chloro-1.3-.5- triazinylamino-(6)l-3-phenyI coumarincan be obtained in an analytically pure form. The purified productis a yellow crystal powder which melts at 199-200. In alcoholic solutio'nthe new compound has a strong. blue fluorescence, in benzene or acetone solution ithas a strong blue-violet fluorescence. Because of its good fluorescence. properties, favourable solubilityorganic substances andrelatil'vely good-stability to light, the new compound is suitable for not only the optical brightening of synthetic materials such as, e'.gl vinyl and vinylidene polymers, polystyrenes, polyethylenes but also for the brightening of certain synthetic textile fibres. For example, if'Dacron fabricof'y'ellowish appearance is treated with 0.025-0.l.% of this triazinyl derivative then the fabric has a much better appearance in daylight than the untreated fabric.

If' in. this example the cyanuric chloride is replaced by cyanuric bromide then '7'-[2-diethylamino-4 bromo-I.35- triaziny1amino+('6)1-3-phenyl coumarinis obtained in an analogous manner. Also' if the 23.7 parts of 7-ami'nof- 3-phen'yl' coumarin are replaced by 25.1. parts of. 7-amino- 3' -(m-methylphenyl)'rcoumarin (M.P. 227-228" then 7 [2 diethylamino -.4 chloro. 113.5 triazinylamino- ('6 )T-S-(m-methylphenyl) coumarin which melts at 18.7--- 18 8 is obtained in. an analogous manner. This product also has a strong fluorescence in inorganic :solution and is suitable for the brightening. of organic materials.

If in' this example the. 15.5 parts of diethylamine are replaced by 21 parts of dipropylamine or 27 parts of dibutylamine, then 7-[2-dipropylamino-4-chl0ro-1.3.5-tri azinylamino-(fi') l-3-phenyl coumarin (M.P. 183-184) or 7- [2-dibutylamino-4-chloro-l .3.5-triazinylamino-'(6) l- 3-phenyl coumarin (M.P. 139140) are obtained respectively. They can also be used for brightening. of organic materials.

10 parts of a polyester fabric of the trade name Dacron having a yellowish appearance are treated for 30 minutes at 9S-100 in a bath (liquor ratio 1:50) containing 0.005 part of '7'-[12 diethylamin0-4-ch10rO-L35 triaziny1ami'no-(6)I-3-pl1eny1 coutnarin as Well as 0.25 part of an olein alcohol pentadecyl glycol ether. The fabric is thenrinsed and dried. In daylight it has a considerably more white appearance than the corresponding untreated fabric.

The same brightening eifect can be attained by the 7- [2 diethylamino 4 chloro 1.3.5. triazinylamino (6)l-3-(mnnethylphenyD-coumarin also mentioned in this example. Also 7-[2-diethylamino-4-chloro-1.3g5-tri- -aziny lamino-(6)']-3-(o-chlorophenyl) coumarin (colourlesscrystal's', M.P. 207-208.) produced in an. analogous manner producesa good brightening efiect on polyester fibres. The latter compound has a clearly more violet fluorescence. than the first named blue fluorescent products.

Alsosynthetic materials can be brightened with the above triazinyl derivatives according to the application methods described in Examples 1, 2 and 5.

23.7 parts of 7-amino-3-phenyl coumarin are reacted as describedin Example 3 with 18.45 parts of cyannric chloride and the 7-[2.4-dichloro-1.3.5-triazinylamino- (6)1-3-phenyl coumarin obtained is isolated by filtering off under suction, washing with water and acetone and drying. The dichlorotriazinyl derivative is fairly diificult to dissolve in organic solvents and it melts at 350 while becoming darker in colour.

77 parts of this dichloro-derivative are suspendedin 750 parts by volume of ethylene glycol monomethyl ether and concentrated aqueous ammonia solution is added dropwise at -10 until phenolphthalein paper turns red. The mixture is heated while stirring at 7075 and stirred for an hour at this temperature while maintaining the alkalinity by the dropwise addition of further amounts of ammonia solution. A pale yellowish, viscous suspension of the 7-[2-amino-4-chloro-1.3.5-t1iazinyl-(6)amino]-3- phenyl coumarin formed is obtained. After cooling, this intermediate product is filtered off under suction, washed with alcohol and water and dried. The intermediate product dissolves in hot dimethyl formamide with a strong blue fluorescence and it melts at over 330 on decomposition. To react with monoethanolamine, the monochlorotriazinyl derivative is heated in 500 parts of dimethyl formamide with 50 parts of monoethanolamine for 30 minutes, at 120-130 while stirring. A brownish solution which fluoresces strong blue is obtained which also remains clear on cooling to room temperature. The reaction product formed is isolated by distilling oil the greater part of the solvent under reduced pressure and adding about 1000 parts of water to the residue. The pale yellow precipitate is filtered off, washed with water and crystallised from diluted methyl cellosolve. The 7- [2 amino 4 hydroxyethylamino 1.3.5 triazinylamino-(6)1-3-phenyl coumarin obtained melts at 220- 221 and it is a yellowish powder which has an intensive blue fluorescence in alcoholic solution. Because of its afiinity to various substrata, this product is an excellent brightening agent for various textile fibres. For example cotton, wool, polyamide fibres, polyacrylonitrile fibres and cellulose acetate fibres can be brightened therewith.

A product having a similar effect is obtained if in this example the monoethanolamine is replaced by excess di ethanolamine. The 7-[2-arnino-4-diethanolamino-1.35 triazinylamino-(6)l-3-phenyl coumarin so obtained crystallises from methyl cellosolve/ alcohol in coarse yellow prisms which melt at 222-224.

10 parts of polyacrylonit rile fabric of the trade name fOrlon having a yellowish appearance are treated for 30 minutes at 95-100 in a bath (liquor ratio 1:50) containing 0.01 part of 7-[2amino-4-hydroxyethyla1ninol.3.5-triazinylamino-( 6) l-3-phenyl coumarin and 0.5 part of formic acid. After rinsing and dryingfthe material so treated has a considerably more white appearance than untreated material.

100 parts of white woollen knitten goods are washed for 30 minutes at 5055 in 1000 parts of a washing liquor containing 2.5 parts of an alkylaryl sulphonate and 0.05 part of the 7-[2-amino-4-hydroxyethylamino-13.5- triazinylamino-(6)]-3-phenyl coumarin described above,

and then rinsed and dried in the air. Wool of a considerably more white appearance is obtained than if the Woollen goods had been washed without the addition of the brightening agent named.

25 parts of previously bleached wool flannel having a yellowish appearance are treated for 30 minutes at 50- 55 in a dye-bath (liquor ratio 1:30) containing 0.05 part of 7-[2-amino4-dietha.nolamino-1.3.5-triazinylamino- (6)1-3-phenyl coumarin and 0.5 partof formic acid and the goods are rinsed and dried. The wool so treated has a considerably higher degree of whiteness than the untreated wool.

- The following six compounds which can be produced in an analogous manner from the corresponding starting materials, also have a good brightening effect on the textiles mentioned:

7 [2 amino 4 diethylamino 1.3.5 triazinylamino (6)]-3-phenyl coumarin yellowish powder, M.P. 211- 212;

7 [2 amino 4 hydroxyethylamino 1.3.5 triazinylamino-(6) ]-3-(m-methylphenyl)-coumarin, yellowish powder, M.P. 204206; I

7 [2 amino 4 hydroxyethylamino 1.3.5 triazinylamino( 6) ]-3-(o-chlorophenyl)-coumarin, almost colourless powder, M.P. l96198;

7 [2 amino 4 methylamino 1.3.5 triazinylarnino (6)1-3-phenyl coumarin, yellow powder, M.P. 280- 282";

7 [2 amino 4 propylamino 1.3.5 triazinylamino (6)]-3-phenyl coumarin, yellowish powder, M.P. 190- 191;

7 [2 amino 4 morpholino 1.3.5 triazinylamino (6)1-3-phen'yl coumarin, yellowish powder, M.P. 286- 287 a 7 Both in solution and on the fibre, the o-chlorophenyl derivative has a more clearly violet fluorescence than the other products mentioned in this example.

Example 5 [O] CH t s 43 00 N /CNH O C-N 77 parts of 7-[2.4-dichloro-1.3.5-triazinylamino-(6)]- S-phenyl coumarin obtained according to Example 3 are suspended in 750 parts of methyl Cellosolve and morphol-ine is added dropwise at 2030 while stirring until a sample dropped onto damp phenolphthalein paper clearly turns red. The yellowish suspension is heated While stirring to -ll5 and stirred for 30 minutes at this temperature while maintaining thealkaline reaction by successive additions of morpholine. The yellow crystal paste is then allowed to cool and the 7-[2.4-dimorpholino- 1.3.5-triazinylamino-(6)l-3-phenyl coumarin formed is filtered off under suction. '.The product is purified by washing with alcohol and recrystallising from about 25 times the amount of chlorobenzene. The new coumarin derivative, a yellow crystal powder which melts at 275 276, has a vivid blue to blue-violet fluorescence in acetone or ethyl acetate and is excellently suitable for the brightening of various polymeric synthetic materials.

A product which is also a valuable brightening agent for'polymeric synthetic materials is obtained if in this example the morpholine is replaced by excess N-ethylbutylamine. The 7-[2.4 bis (N-ethylbutylamino)-1.3.5-

triazinylamino-( 6) -3 phenyl coumarin so obtained forms pale yellow fine crystals which melt at 127-129. In a1- coholic solution the product has a blue and in benzene solution it has a blue-violet fluorescence.- It has the advantage over the morpholine derivative that it. has much better solubility in organic solvents and plasticising agents. 0.07 part of 7-[2.4-dimo-rpholino-L3j triazinylamino- (6) J-S-phenyl coumarin are gelatinised on a set of mixing rollers at 160 for 15 minutes .with a mixture consisting 'of armresof polyvinyl chloride powder," 33'-parts of ldioctyifphthal at'e, 2* parts of dien-butoxy tin dilaurate and 033 parts of so'diinn penta'pct'yl tripolyphosphate and then drawnout into foils; The polyvinyl chloride foils pro- "duced in this way have a considerabiy'more white appearance-indaylight than the corresponding fo'ils produced without the addition of brightening agent. H )'5" part or 7-'E2.4 bis=(N-ethylbdtylamino);113.i tri- "aziny1amino-f6)"-J-3;phenyi eeumarin; 7 parts or titanium dioxide (finatas), 67 parts of polyvinyl chloride, 33 parts 'of-tfi'octyi pirthalatje; 2 parts of" dib'utyI- tin dila'urate and &? parts of sodium penta-octyl tripoiyphesphare are workedup in the manner described above into an opaque jibi-i. The. fei-I- soprednced has a much whiter appearance than a comparative sample produced without brightening agent- V v 'Ifnthe same-way,- for exaniple; also the compounds listed'in the following table can be used for the brightenp'olyvinyl pioneers:

tained becomes thinly liquid. It isthen slowly heated to room temperature and stirred over night at this temperature. To complete the reaction, the yellow suspension is boiled under reflux at IOU-410 for 23 hours while stirring. The reaction product is isolated in the usual way by evaporating under reduced pressure or precipitating with water, washed with Water and purified by recrystallising from ethylene glycol monomethyl ether, ethyl alcohol or dimethyl formamide/ ethyl alcohol. The 7 [2.4 diethylamino 1.3.5 triazinylamino (6)] 3- phenyl coumarin obtained forms a. finely crystalline powder which melts at 264-265". The new compound, which has a vivid blue fluorescence in alcoholic solution, can be usedfor the brightening of acetate silk and polyamide fibres.

The same product is-obtainedif 23.7 parts of 7-amino-S- phenyl coumarin are reacted according to the process described in Example 2 with excess parts) of 2.4-bisethylamino-G-chloro-l.3.5 triazine ((Thurston, Am. Soc. 73, 2982 (1951)) in 250 parts of dimethyl formamide or dimethyl: sulphoxidc.

10 parts of pale yellowish nylon fabric are treated for 30 minutes at in a dyebath (liquor ratio 1:40), which contains 0.01 part of 7-E2.4'diethylamin'0-1'.3.S-triaZinylamino-(6)l-3apheny1 coumarin and 0.2- part of formic acid After rinsing and drying, the material so treated has a much more white appearance than before treatment.

10 parts of undyed acetate silk yarn are treated at The compounds listed in this table can be produced by themethod described inthis example or in Example 7.

77 parts of the 7--;II2.4-dielilorotriazinylaminim(6)l-fl phenyl-coumarin obtained according to .Example' 3' are suspended lHLSQO' parts oddimethyl formamide and at one? 69- .parts of a 70% aqueous ethylannne solution in a bat-h (liquor rat'ib' me containing 0.0025 part of the -tria'zinyl compound mentioned above. After rinsing and drying, the yarn so treated has a much more White appearance than before treatment. 7

part-s ofundyed nylon material are washed at 70? in awashing' liquor Clique-r ratio 1:10) containing 0 .0S .parts of the brightening agent described above and 8 g./litre of a synthetic washing agent, for 30' minutes, and then tinsed and dried. The fabric so treated has a much more brilliant appearance than a fabric washed without the addition of the brightening agent;

Thecomp ounds listed in the following table which. can all: be produced by the method described in this example, can be used in an analogous manner for example for are added while stirring. The thickly liquid paste ob- 76 the brightening of polyamide and acetyl cellulose fibres.

2,945,033 '11 '12 TABLE Example 8 General formula: 111mm): g

=N \OA N/ C-NH- 3 0 N /CNH I \(IJN/ Q on X 8.43 parts of 7-[2-diethylamino-4-chloro-1.3.5-triazinylam-ino (6)]-3-phenyl coumarin are boiled under reflux in 160 parts of glacial acetic acid for 20 hours. The X Ar Appearance -l chlorotriazine derivative gradually dissolves and towards egms the end the 7-[2-diethylamino-4 hydroxy-1.3.5-triazinylamino-(6)]-34phenyl cournarln begins to form as a pale fifigjfig i fififith' l rgd' r i i "g ffl l iii lifiiyellow precipitate. After cooling, the product is filtered -NHOQH5 p-chlorophenyL. yellow powder. 288-289 off, washed with alcohol and purified by recrystallising NHCmCmOL 263-265 from dimethyl formamide/alcohol. The pure com- 182 pound is an only pale yellowish coloured crystal powder H; which melts at 315-316.. The new ooumarin derivado pale yellow powdeh 156457 tive does not dissolve un org amc solvents as well as the corresponding chloro-derlvatlve.

If in this example the 7-[2-diethylamino-4-chloro- N(GHzCHzOH)1 do pale o llowish 227-228 1.3.5-triazinylamino-(6)]-3-phenyl coumaril:1 repl7a Ee2d b 2amino-o-met-h l hen lamino com oun en 2 y yp y p vNHcHzomoH" 5 122 3? yellow powder 211 213 (o-methylphenylamino)-4 hydroxy 1.3.5-triazmylami- NCH1OHZOH figf g 164466 no-(6)]-3-phenyl coumarin (M.P. 340) is obtained as 1 CH3 p a pale yellowish powder. Both the above products can N(CHzCHgOH)2 md yellowish powdehn 2154215 be used according to Example 5 for bnghtemng polyvlnyl chloride products.

Example 9 N Example 7 IIMCHQ g (C2315): CzN C f.l=N V N GNH N C-NH CH=C 0 6 0 (H; NHCzHs I ll 0 4 8.43 parts of 7-E2-diethylam1no-4-chloro-L3.S-trramnylamino-(6) ]-3-phenyl coumarin are added to a solution 8.43 parts of 7-[2-d-iethylamino-4 chloro-1.3.5-triazi- 0f 4 parts of Phenol and 046 P of Sodmm Pa nylamino-(6)]-3-phenyl coumarin obtained according to y volume of y a o t t whole a ell d Example 3 are suspended in 75 parts of ethylene glycol under reflux for 2 hours Wh 11e After d-lstllllng monomethyl ether and 2.5 parts of 70% aqueous ethyl- Off butanol, the residue 18 With Water a amine solution are added. The mixture obtained is little h l and it can be purified by recrystfllhsm; boiled under reflux for 30 minutes while stirring and the q 7-[2-dlethylammo P Y- 7-[2-diethylamino-4-ethylamino 1.3.5 triazinylaminoy )1- -p y m n 1S Obfamed 8 a (6)1-3-phenyl cournarin is isolated by precipitating from P yellowish Powder Winch melts at 196-198. The the clear, strongly blue-fiuorescing solution with water. W p q fluoresces 111 Organic 501M101} blue to 171116- On reorysnallisin fr hot t l th l i ll pure violet depending on the type of solvent and it can be used product is obtained as pale yellow little-crystals which for brlghtenlllg of Organic melt at 171- 172. If in this example the phenol 1s replaced by 4.2 parts The compound is suitable among other things for the 0f lg q then 7 -[2-difitl'lylalninfl-4'PhenylmemaptoL optical brightening of cellulose diand tni-acetate prod- Y 'P Y 6011111211111 ucts. 169) ls obtained as pale yellow crystals.

10 parts of undyed, pale yellowish cellulosetriacetate The following Va1111b1e Phenol Thiophenol tfabric are treated for 30 minutes at 95-100 in a dyebath fives can be Produced 111 analogous manner! (liquor ratio 1:50) containing 0.02 part of 7-[2-diethyl- 7-[2-diethylamjno-4-(p -methylphenoxy) 1.3.5-triaziny1- arnlno-4-ethylarnmo-1..5-trlazlnylamlno (6)]-3-pheny (6)-lamin ]-3-pheny1 coumarin, pale yellowish crystals, coumarln. After rinsing and drying, the trlacetate fabric 1894910, has a. considerably more white appearance than. before 7- 2 i 1;h 1amino-4-(p-chlorophenoxy) 1.3.5-triaZin 1. treatment (6)-amino]-3-phenyl coumarin, pale greenish yellow Also the followlng optlcal brightening agents for exneedles, p 4 4 ample F according to the m 7-[2 diethylamino 4 (3.4 dichlorophenylmercapto)- scrlbed in this example, can be used for the optlcal brlght- 1 1.3 5 triaZiny1 (6) amino] 3 phenyl coumarin, pale enlng of cellulose trlacetate substances: yellowish crystals, M'P.

'7-[2-diethylamino-4 hydroxyethylamino 1.3.5-triazinyl- 0.2 part of 7-[2-diethy1amino-4-phenoxy-1.3.5-triaziamino-(6)1-3-phenyl coumarin, yellow powder; M.P. nylamino-(6)]-3-phenyl coumarln, parts of acetylcel- 192 194", I lulose and 25 parts of diethyl phthalate are dissolved in 7-[2-d1ethylamino 4 diethanolamino 1.3.5-triazinyl- 900 parts of acetone. The solution obtained is poured ammo-(6)1-3-phenyl coumarin, yellow powder, M.P. onto glass plates and, after evaporating ofi the acetone, 128 (as monohydrate), M.P. of the anhydrous subtransparent films which can be drawn off the glass plates stance: 178-179". 75

are obtained. In daylight these plates have a more brilliant appearancelthan corresponding films produced with out the addition of the brightening agent named.

Opaque cellulose acetate films are produced by adding partsof AnatasJ-to the above mixture before pouring it onto the glass plates. The opaque films obtained are I Example C-NH 3815 parts. of 7-[2.4 dichloro- 1.3.5-triazinylamino- (6)1-3-phenyl coumarin obtained according to Example 3 are suspended in 500 parts of ethylene glycol monomethyl ether and ammonia in gas form is introduced at 20-30 until a sample dropped onto damp phenolph-thalein paper shows a clear reddening. The whole is heated to 120-130 while maintaining this alkalinity by the introduction of further amounts of ammonia, and is stirred for 10 hours at this temperature the alkalinity being maintained as described above. After cooling, the pale yellowish coloured precipitate is filtered off, washed with alcohol and water and dried at 80". The 7-[2.4-diarnino-l.3.5atriazinylamino-(6 )l 3 phenyl coumarin so obtained dissolves in dimethyl formam-ide or methyl cellosolve with a strong blue fluorescence. The product crystallises from dimethy-l formamide-aloohol' in pale yellowish fine aggregates which melt at 311-312". The new com-pound can be used for example for the brightening of cellulose fibres.

0.001 part of 7-[2.4-diamino 1.3.5 triazinylamino- (6) ]-3-phenyl coumarin are dissolved in 1 part of hot dimethyl forrnamide or ethylene glycol monomethyl ether and the solution is poured at 70 80 into 400 pants of water. 10 parts of white cotton poplin are treated for minutes at 708'0 with the blue fluorescent dispersion so obtained. Afiter rinsing and drying the cotton so treated has a. much more white appearance in daylight than before treatment.

3.46 parts of 7-[2.4 diamino 1.3.5triazinylamino- (6)1-3-pheny-l coumarin obtained according to Example 10 are added while stirring to. 30 parts of 37% aqueous formaldehyde solution, 4 partsof sodium carbonate are added. and the whole is stirred tor 10 hours ,at 60-65 lAfter cooling; unchanged starting material is filtered ofi and the reaction product corresponding roughly to the above formula is. isolated by evaporating in the vacuum or by precipitating fi'om the yellow filtrate with water.

-The methylol: compound obtained is a yellow powder,

the softening point of which is 150. The compound is -'more easily soluble in solvents containing hydroxyl groups such as, e.g. ethylene glycol monomethyl ether, as the diamino compound not reacted with formaldehyde and like that compound, it can be used.- for the brightening of cellulose fibres.

77 parts of 3-phenyl-7-[2.4 dichl0ro-1.3.5-triazinylamino-(6)]-coumarin obtained according to Example 3 are well distributed. while stirring in a mixture of 960 parts of acetone and parts of water and 21.4 parts of o-toluidine and 22 parts of sodium carbonate are added one after the other at 20-30. The yellowish suspension is stirred for 24 hours at room temperature, after which time the toluidine has practically disappeared.

500 parts of water are added while stirring to the reacsolution of the compound has a strong blue fluorescence.

10 parts of yellowish nylon .fiabric aretreated for 15 minutes at 75 irra dyebath (liquor ratio 1:50) which contains 0.005 part of the triazine derivative named above as well as 0.25 part of a condensation product from olein alcohol and 15 mols of ethylene oxide. After rinsing and drying the material so treated has a much "more white appearance than before treatment.

1 TABLE General formula:

N C-NH CO X appearance MLP.

m-methoxyanilinoe. yellbwish crystals..-" 209-21?v mchloranilino do 227-228" on decomposition. p-chloranilme pale yellow powder 270-273 on decomposition. o-ethoxyanilino .do fill-212. 2-hydroxy-eyclohexylpale yellow crystals.-. -178.

ammo. B-phenylethylamino yellow crystals. 183-185". monoethanolamino yellow powder 230-232". diethan olamino pale'yellow prisms-. 225-227? on decomposition. ethylamino pale yellow crystals.-. 248-250"; th1azolyl-(2)-amino yellow powder over 300 on decomposition. 4.5-d1 hydro-rmidazolyl-(2).- do over 365 on deammo. composition. pyridyl-(2)-a.miuo do decomposes over 330. tetrazolyl-(5)-amino do decomposes over 365. 1.2.4-triazolyl-(3)- amino do decomposes over 365.

2,945,033 15 16 Examplel3 2 4. The 7-triazinylamino-3-phenyl 'coumarm of the formula: i a m CE 3 NH 7 CH I N: \CNH /CO 6 W 1 V I do \C=N O Y N G-NH I .C4Hn "1 I El 42.2 parts of 7-[2-diethylamino-4-chloro-1.3.5-triazinyl- E amino-(6)1-3-phenyl coumarin obtained according to The 7-tI'1aZlnY1am111W3"Phenyl coumarln O the Example 3 are boiled under reflux While stirring in a fQrmlllai solution of 2.3 parts of sodium in 300 parts by volume v v i 7 CH of n-butyl alcohol for 1 hour. The precipitated sodium chloride is filtered ofi, the solution obtained is evaporated J=N v to dryness in the vacuum at Water bath temperature and CO the residue is recrystallised from benzene/petroleum ether. The 7- [2-diethylamino-4-butoxy-1 .3 .5 -triazinylamino-(6)]-3phenyl coumarin which crystallises into N(C:Hs)a

yellowish coloured prisms melts at 158-160 and, in

6. The 7-triazinylamino-3-phenyl coumarin of the benzene solution, has a viv1d blue-violet fluorescence.

formula: If in this example, the n-butyl alcohol is replaced by n-propyl alcohol, then 7-[Z-diethylamino-4-propoxy-1.3.5- 7 CH triazinylamino-(6)J-B-phenyl cournarin is obtained in an IIIHI I analogous manner. It melts at 181 and has the same C= fluorescent properties. 00

Both these triazine derivatives can be used for the y brightening of polyvinyl chloride synthetic materials according to Example 5. HOGHaCHaNH What I claim is:

7. The 7-triazin lamino-3- hen l cournarin of the Y -P yl coumarins of the formula y p y wherein X stands for a member selected from the group 40 0 conslstrng of am no, alkylammo, lower dialkylamino, N cyclohexylarnino, monoethanolamino, diethanolamino, r N-phenylamino, morpholino, piperidino, Cl, Br, hydroxy,

lower alkoxy, phenoxy, lower alkylphenoxy, chlorophen- 'f oxy, phenylthio; chlorophenylthio, hydroxycy clohexylarnino, lower alkylaminoalkylamino, N-lower alkylphenyl- 8. The 7-triazinylamjno-3-phenyl coumann of the amino, N-lower alkoxyphenylamino, N-chlorophenylamiformula: V no, benzylamino, N-pyridylamino, -N-thiazolylamino, C CE N-dihydro-imidazolylamino, N-triazolylamino and N-te'te11 razolylamino,- Z stands for a member selected from the group consisting of amino, alkylarnino, lower dialkylamino, cyclohexylamin'o, monoethanolamino, diethanol- -NH amino, N-phenylamino, morpholino and piperidino, and N A represents a member selected from the group consisting of phenyl, chlorophenyl, methylphenyl and dimethyl- HHG=NOH1OHIOH1CEB phenyl. 1 m f the 2. The 7-triazinylamino-3-phenyl coumarin of the 3 52? 7 mazinylammo 3 pheny cou arm 0 formula:

N O H N(C2Ho)z /C 0 a \C I G 0:: 1 C: p CO 00 N CNH N CNH O N O V 7 v v JC-N V 2 H V, 4 2 5)n I f th' at at 3. The 7-triazinylamino-3-phenyl coumarrn of the References Cited the file 0 is p e FOREIGN PATENTS formula.

. CH 7 518,213 Canada, Nov. 8, 1955 f x 723,288 Great Britain l Feb. 2, 1955 o- C=N v I NH OTHER REFERENCES o Landolt: American Dyestufl Reporter, pp. 353-356,

April 18, 1949. M01 5): Goodwin: Arch. Biochem., vol. 27(1950), pp. 152-173. 

1. 7-TRIAZINYLAMINO-3-PHENYL COUMARINS OF THE FORMULA
 7. THE 7-TRIAZINYLAMINO-3-PHENYL COUMARIN OF THE FORMULA: 